CN107987552A - A kind of preparation method and applications of water-soluble natural pigment microcapsule - Google Patents
A kind of preparation method and applications of water-soluble natural pigment microcapsule Download PDFInfo
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- CN107987552A CN107987552A CN201711268123.3A CN201711268123A CN107987552A CN 107987552 A CN107987552 A CN 107987552A CN 201711268123 A CN201711268123 A CN 201711268123A CN 107987552 A CN107987552 A CN 107987552A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a kind of preparation method of water-soluble natural pigment microcapsule, the method of the present invention is used as wall material using methyl methacrylate and acrylic acid or acrylamide, using water-soluble natural pigment as core, add emulsifying agent, initiator, by being prepared by mixing into lotion under certain condition, microcapsule product is obtained by polymerization.The method of the present invention preparation process is environmentally protective, and easy to operate, and obtained microcapsules stabilization, acid and alkali-resistance, light fastness are excellent, can be used for field of textiles as mill base.
Description
Technical field
The invention belongs to textile raw material technical field, and in particular to a kind of preparation side of water-soluble natural pigment microcapsule
Method and its application.
Background technology
Natural pigment both generally is from animal, plant tissue, therefore, in general higher to the security of health.
Inherently a kind of nutrient of some natural pigments, has nutritive validity, and part also has certain pharmacological action.Natural pigment
The color of natural goods can also preferably be imitated, tone during coloring is more natural.But because being extracted from natural goods,
Therefore component is coexisted by it sometimes to be influenced or itself just have peculiar smell, and pigment concentration is typically small, and dieing activity is poor, some natural
Edible coloring agent even occurs chemical reaction with raw-food material and changes colour, its fastness is poor, by pH value, oxidation, illumination, temperature
Etc. having a great influence.
Microcapsules refer to coat core (solid, liquid or gas) using natural or synthetic high molecular material,
The diameter of formation is from nanometer to several microns even hundreds of microns of nucleocapsid structure small container.The core wall construction of microcapsules can be with
Core is isolated with external environment, protects it from the influence of many factors such as the oxygen, high temperature, ultraviolet in the external world.Therefore, utilize
The higher weatherability of wall material, can more sufficient core weatherability it is poor the defects of.
Natural pigment strong coloring force, it is safe and non-toxic, it can be widely used as colouring agent by food service industry, be most to develop
The food additives of value, have a variety of different physiological functions.Microcapsules refer to utilize core (solid, liquid or gas)
Natural or synthetic high molecular material cladding is got up, and the diameter of formation is from nanometer to several microns even hundreds of microns of core-shell structure copolymer knot
Structure small container.The core wall construction of microcapsules can isolate core with external environment, protect it from the external world oxygen, high temperature,
The influence of many factors such as ultraviolet.
At present, pigment is made microcapsules as core to have been applied in food service industry, and the later stage is focused in part
Smell and relatively low lasting type microcapsules are required to quality of colour.But since part natural pigment Nature comparison is active, chemistry is anti-
Answering property is stronger, and light and heat can promote its oxygenolysis and lose coloration ability, has seriously affected the color fastness of coloring, and shows
There is micro capsule technology to be difficult to meet it toward the needs of other field large-scale promotions again, it would be highly desirable to solve.
The content of the invention
In view of the above-mentioned problems, the present invention provides a kind of preparation method of natural pigment microcapsules, by polymerizeing water solubility
Natural pigment is wrapped in the high molecular polymer of methyl methacrylate, improves the resistance to photo-thermal and acid and alkali-resistance of natural pigment
Property, field of textiles can be used for as mill base.
To solve above technical problem, the application is achieved through the following technical solutions：
A kind of preparation method of water-soluble natural pigment microcapsule, comprises the following steps：
（a）A certain amount of natural pigment, emulsifying agent and deionized water are mixed, and control mixing speed at 400~1100 revs/min,
Heating water bath is uniformly mixed to 50~80 DEG C and obtains natural pigment microemulsion at the same time；
（b）A certain amount of initiator is added, adds a certain amount of methyl methacrylate, after mixing, is warming up to 80~90
DEG C, 1~3h of isothermal reaction；
（c）Be slow added into a certain amount of second comonomer, while 80~90 DEG C of water-baths effects, continue 400~1100 turns of rotating speed/
Point（It is basically identical with step a rotating speeds）2~5h of lower reaction, that is, obtain water-soluble natural pigment microcapsule of the present invention.
Preferably, the methyl methacrylate, second comonomer, emulsifying agent, deionized water, natural pigment and initiator it
Between mass ratio be 100：10~50：10~50：1500~2500：25~100：1~2.
The natural pigment is water-soluble natural pigment, preferably grape skin color, red sorghum pigment, Cochineal color,
The fluffy sweet tea haematochrome of gardenia blue pigment, alkali, water-soluble annatto pigment, radish red pigment, grape skin red pigment, Ipomoea batatas(L.)Lam,
Mulberry red pigment, haematochrome of red rice, indigo fruit pigment, Cacao pigment, chrysanthemum uranidin, water soluble tea marennin and tea yellow
At least one of element.
Preferably, the emulsifying agent is the composite emulsifier of span60 and tween80, or span80 and tween60
Composite emulsifier, mass ratio of its HLB value between 3~10, Si Pan and tween can be calculated according to HLB formula.
Preferably, the initiator is at least one in benzoyl peroxide, dilauroyl peroxide and azodiisobutyronitrile
Kind.
Preferably, the second comonomer is at least one of acrylic acid and acrylamide.
The present invention has following positive beneficial effect：
（1）The present invention makees reaction medium with water, and pigment source enriches, and makees polymerization protection system using cheap emulsifying agent, and
Easy to operate, technique is simple, environmentally friendly.
（2）The present invention can control particle size by stir speed (S.S.), and at 0.1~8 μm, operation is more easy to be controllable, can
The required product of stable production, later stage can be preferably applied in industrial production.
（3）Second comonomer used in the present invention is water miscible, can preferably dissolve each other with water miscible pigment, draw in oil-soluble
Methyl methacrylate can be reacted with acrylic acid or acrylamide under the action of sending out agent, and generation polymer is more preferable by water colo(u)r
Ground wraps up.
（4）Core is safe and non-toxic used in the present invention, environmentally protective, and wall material resistance to acid and alkali is good, transparency is high, can effectively protect
Protect natural pigment, so as to get microcapsules there is bright-colored, good weatherability, applied to original liquid coloring not only energy-saving ring
Protect and color fastness is high, meet the development trend of dyeing, there is vast potential for future development.
Brief description of the drawings
Fig. 1 is the confocal laser of the fluffy sweet tea haematochrome microcapsules of 2 gained alkali of embodiment away from microscopical direct view.
Embodiment
Invention is further described with reference to specific embodiment, certain following embodiments should not be construed as to this hair
The limitation of bright protection domain.
Embodiment 1
A kind of preparation method of water-soluble natural pigment microcapsule, comprises the following steps：In the three-necked flask that capacity is 250mL
90mL water, 1g gardenia blue pigments, 0.6g Span60,0.4g Tween80 are added, 65 DEG C is warming up to and is stirred in 400r/ min
20min obtains gardenia blue pigment microemulsion, and methyl methacrylate 4g is added dropwise, and adds benzoyl peroxide 0.05g, 80 DEG C of constant temperature
React 2h.1g acrylamides are added dropwise again, 80 DEG C of isothermal reaction 3h, obtain the micro- glue of gardenia blue pigment that average grain diameter is 6.331 μm
Capsule.
Embodiment 2
A kind of preparation method of water-soluble natural pigment microcapsule, comprises the following steps：In the three-necked flask that capacity is 250mL
60mL water, the fluffy sweet tea haematochrome of 2g alkali, 0.3g Span60,0.2g Tween80 are added, 70 DEG C is warming up to and is stirred in 500r/ min
20min obtains the fluffy sweet tea haematochrome microemulsion of alkali, and methyl methacrylate 4g is added dropwise, and adds azodiisobutyronitrile 0.08g, 85 DEG C of perseverances
Temperature reaction 3h.Acrylic acid 2g, 85 DEG C of isothermal reaction 3h are added dropwise, obtain the fluffy micro- glue of sweet tea haematochrome of alkali that average grain diameter is 2.562 μm
Capsule.
Embodiment 3
A kind of preparation method of water-soluble natural pigment microcapsule, comprises the following steps：In the three-necked flask that capacity is 250mL
80mL water, 1.5g chrysanthemums uranidin, 0.6 span80 and 0.4 tween60 are added, 60 DEG C is warming up to and is stirred in 600r/ min
10min obtains chrysanthemum uranidin microemulsion, and methyl methacrylate 4g is added dropwise, and adds benzoyl peroxide 0.07g, 80 DEG C of constant temperature
React 2h.Acrylic acid 2g, 80 DEG C of isothermal reaction 2h are added dropwise, obtain the Chrysan Yellow pigment microcapsule that average grain diameter is 1.164 μm.
Embodiment 4
A kind of preparation method of water-soluble natural pigment microcapsule, comprises the following steps：In the three-necked flask that capacity is 250mL
70mL water, 3g mulberry red pigments, 0.3 span80 and 0.2 tween60 are added, 70 DEG C is warming up to and is stirred in 700r/ min
30min, obtains mulberry red pigment microemulsion, and methyl methacrylate 4g is added dropwise, and adds azodiisobutyronitrile 0.08g, 85 DEG C of perseverances
Temperature reaction 1h.Acrylamide 1.5g, 85 DEG C of isothermal reaction 2h are added dropwise, it is micro- to obtain the mulberry red pigment that average grain diameter is 0.635 μm
Capsule.
Embodiment 5
A kind of preparation method of water-soluble natural pigment microcapsule, comprises the following steps：In the three-necked flask that capacity is 250mL
80mL water, 1.5g haematochrome of red rice, 0.6 span80 and 0.4 tween60 are added, 60 DEG C is warming up to and is stirred in 1000r/ min
30min obtains haematochrome of red rice microemulsion, and methyl methacrylate 4g is added dropwise, and adds benzoyl peroxide 0.06g, 80 DEG C of constant temperature
React 2h.Acrylic acid 2g, 80 DEG C of isothermal reaction 2h are added dropwise, obtain the haematochrome of red rice microcapsules that average grain diameter is 0.526 μm.
Comparative example 1
The fluffy sweet tea haematochrome microcapsules of alkali are prepared with reference to CN106173818A specifications embodiment 4.
The fluffy sweet tea haematochrome of former alkali, embodiment 2 and the fluffy sweet tea haematochrome microcapsules of 1 gained alkali of comparative example are subjected to application test：
（1）The fluffy sweet tea haematochrome of former alkali, comparative example 1 and the fluffy sweet tea haematochrome microcapsules 0.05g of 2 gained alkali of embodiment are taken respectively, are respectively added
Enter the dissolving of 10ml absolute ethyl alcohols, then plus distilled water is settled to 100ml, and using 10% ethanol solution as blank control, measure is former
The fluffy sweet tea haematochrome of alkali, comparative example 1 and the fluffy sweet tea haematochrome microcapsules of 2 gained alkali of the embodiment absorbance at wavelength 535nm, take respectively
Two kinds of solution of 20ml, use H2SO4(1mol/L) and NaOH（1mol/L）The pH for adjusting solution is respectively 1,14, in the process
Pay attention to lucifuge.After 1h, using 10% ethanol solution as blank control, its absorbance is tested respectively at wavelength 535nm, calculate
The loss late of the fluffy sweet tea haematochrome of alkali, studies influences of the different pH to the fluffy sweet tea haematochrome of different disposal alkali, the results are shown in Table 1：
The loss late of the fluffy sweet tea haematochrome of alkali and microcapsule product under the different pH value of table 1
| pH | 1 | 14 |
| The former fluffy sweet tea haematochrome of alkali（%） | 60.2 | 70.5 |
| Comparative example 1（%） | 15.3 | 17.2 |
| Embodiment 2（%） | 3.1 | 5.3 |
As it can be seen that being lost by the fluffy sweet tea haematochrome of alkali of microencapsulation of the present invention almost without pigment, its resistance to acid and alkali significantly improves.
（2）The fluffy sweet tea haematochrome of former alkali, comparative example 1 and the fluffy sweet tea haematochrome microcapsules 0.05g of 2 gained alkali of embodiment are taken respectively,
Each to add the dissolving of 10ml absolute ethyl alcohols, then plus distilled water is settled to 100ml, using 10% ethanol solution as blank control, surveys
Determine the fluffy sweet tea haematochrome of original alkali, comparative example 1 and the fluffy sweet tea haematochrome microcapsules of 2 gained alkali of the embodiment absorbance at wavelength 535nm, point
Two kinds of solution of 20ml are not taken, is positioned under sunlight and irradiates 0h, 2h, 8h, 12h, 24h respectively, and blank is used as using 10% ethanol solution
Control, tests its absorbance respectively at wavelength 535nm, calculates the loss late of the fluffy sweet tea haematochrome of alkali, studies different light application times
Influence to the fluffy sweet tea haematochrome of different disposal alkali, the results are shown in Table 2：
The loss late of the fluffy sweet tea haematochrome of alkali and microcapsule product under the different light application times of table 2
| Light application time（h） | 0 | 2 | 8 | 12 | 24 |
| The former fluffy sweet tea haematochrome of alkali（%） | 0 | 4.6 | 48.6 | 60.7 | 71.2 |
| Comparative example 1（%） | 0 | 2.8 | 28.3 | 39.7 | 45.9 |
| Embodiment 2（%） | 0 | 1.3 | 11.5 | 13.5 | 16.7 |
As it can be seen that the fluffy sweet tea haematochrome of alkali is handled by microencapsulation of the present invention, the stability to light is significantly improved.
The present invention is described in detail above in conjunction with embodiment, still, person of ordinary skill in the field can
Understand, can also be to each design parameter make a change in above-described embodiment, shape on the premise of present inventive concept is not departed from
Into multiple specific embodiments, it is common excursion of the invention, is no longer described in detail one by one herein.
Claims (10)
1. a kind of preparation method of water-soluble natural pigment microcapsule, it is characterised in that comprise the following steps：
（a）A certain amount of natural pigment, emulsifying agent and deionized water are mixed, control certain mixing speed, while heating water bath is extremely
50~80 DEG C, it is uniformly mixed and obtains natural pigment microemulsion；
（b）A certain amount of initiator is added, adds a certain amount of methyl methacrylate, after mixing, is warming up to 80~90
DEG C, 1~3h of isothermal reaction；
（c）A certain amount of second comonomer is slow added into, while 80~90 DEG C of water-baths act on, controls certain mixing speed reaction 2
~5h, that is, obtain water-soluble natural pigment microcapsule of the present invention.
2. the preparation method of water-soluble natural pigment microcapsule according to claim 1, it is characterised in that：The metering system
Mass ratio between sour methyl esters, second comonomer, emulsifying agent, deionized water, natural pigment and initiator is 100：10~50：10~
50：1500~2500：25~100：1~2.
3. the preparation method of water-soluble natural pigment microcapsule according to claim 1, it is characterised in that：The natural pigment
For water-soluble natural pigment.
4. the preparation method of water-soluble natural pigment microcapsule according to claim 3, it is characterised in that：The natural pigment
For grape skin color, red sorghum pigment, Cochineal color, gardenia blue pigment, the fluffy sweet tea haematochrome of alkali, water-soluble annatto color
Element, radish red pigment, grape skin red pigment, Ipomoea batatas(L.)Lam, mulberry red pigment, haematochrome of red rice, indigo fruit pigment, cocoa shell
At least one of pigment, chrysanthemum uranidin, water soluble tea marennin and tea uranidin.
5. the preparation method of water-soluble natural pigment microcapsule according to claim 1, it is characterised in that：The emulsifying agent is
The composite emulsifier of span60 and tween80, or the composite emulsifier of span80 and tween60, its HLB value are 3~10.
6. the preparation method of water-soluble natural pigment microcapsule according to claim 1, it is characterised in that：The initiator is
At least one of benzoyl peroxide, dilauroyl peroxide and azodiisobutyronitrile.
7. the preparation method of water-soluble natural pigment microcapsule according to claim 1, it is characterised in that：The second comonomer
For at least one of acrylic acid and acrylamide.
8. the preparation method of water-soluble natural pigment microcapsule according to claim 1, it is characterised in that：Step a and step c
Middle mixing speed keeps basically identical, and upper and lower difference is no more than 50 revs/min, and controls in 400~1100 revs/min.
9. the water-soluble natural pigment microcapsule that any one of claim 1~8 is prepared.
10. application of the water-soluble natural pigment microcapsule in textile coloration described in claim 9.
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| CN201711268123.3A CN107987552B (en) | 2017-12-05 | 2017-12-05 | A kind of preparation method and applications of water-soluble natural pigment microcapsule |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112155146A (en) * | 2020-09-16 | 2021-01-01 | 上海交通大学 | Method for enabling bixin to stably exist in water phase |
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| CN102719145A (en) * | 2012-06-29 | 2012-10-10 | 广州大学 | Disperse dye nanocapsule for thermal sublimation digital printing ink-jet ink and preparation method of disperse dye nanocapsule |
| CN102847497A (en) * | 2012-07-05 | 2013-01-02 | 天津大学 | Preparation method and application of nanometer pigment microcapsule |
| CN103509527A (en) * | 2012-06-21 | 2014-01-15 | 南京工业大学 | Phase change energy storage microcapsule material and its preparation method |
| CN103725106A (en) * | 2013-12-18 | 2014-04-16 | 天津大学 | Preparation method of carbon black water-based color paste for ballpoint pen |
| CN106173818A (en) * | 2016-07-12 | 2016-12-07 | 淮海工学院 | The preparation method of a kind of Herba suadeae glaucae sweet red pigment microcapsule and stability |
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2017
- 2017-12-05 CN CN201711268123.3A patent/CN107987552B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103509527A (en) * | 2012-06-21 | 2014-01-15 | 南京工业大学 | Phase change energy storage microcapsule material and its preparation method |
| CN102719145A (en) * | 2012-06-29 | 2012-10-10 | 广州大学 | Disperse dye nanocapsule for thermal sublimation digital printing ink-jet ink and preparation method of disperse dye nanocapsule |
| CN102847497A (en) * | 2012-07-05 | 2013-01-02 | 天津大学 | Preparation method and application of nanometer pigment microcapsule |
| CN103725106A (en) * | 2013-12-18 | 2014-04-16 | 天津大学 | Preparation method of carbon black water-based color paste for ballpoint pen |
| CN106173818A (en) * | 2016-07-12 | 2016-12-07 | 淮海工学院 | The preparation method of a kind of Herba suadeae glaucae sweet red pigment microcapsule and stability |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112155146A (en) * | 2020-09-16 | 2021-01-01 | 上海交通大学 | Method for enabling bixin to stably exist in water phase |
| CN112155146B (en) * | 2020-09-16 | 2022-11-22 | 上海交通大学 | Method for enabling bixin to stably exist in water phase |
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| CN107987552B (en) | 2019-11-15 |
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